JPH11124465A - Antistatic resin composition containing phosphonium fluorinated sulfonate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition capable of exhibiting excellent heat resistance, transparency and mechanical property by including a thermoplastic polymer and a heat-resistant antistatic agent. SOLUTION: This composition is obtained by mixing (A) an antistatic agent containing a halogenated carbon sulfonate of a multi-substituted phosphonium compound in an amount enough to impart antistatic characteristics with (B) a thermoplastic resin. Phosphonium fluorinated sulfonate is preferable as phosphonium sulfonate of the component A. An aromatic polycarbonate, a polyether imide, a polyester, a polyphenylene ether/polystyrene blend, a polamide, a polyketone, ABS or a blend of these polymer resins is preferable as the component B. Furthermore, the composition preferably comprises 90-99.95 wt.% component B and 10-0.05 wt.% component A.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an antistatic resin composition, and more specifically, to a transparent thermoplastic resin composition comprising a thermoplastic polymer and a halogenated carbon sulfonate of a polysubstituted phosphonium compound. And halogenated carbon sulfonates of polysubstituted phosphonium compounds.

[0002]

BACKGROUND OF THE INVENTION Many polymers or polymer blends are relatively non-conductive. As a result, static charge may accumulate during processing and use of the polymer as it is. Charged polymer moldings attract fine powder dust and can impair a smooth surface condition. Particles attracted to the surface of the molded article may reduce the transparency of the molded article. In addition, electrostatic charges can severely hinder the polymer manufacturing process. In the past, conductive agents or surfactants, such as carbon and metal particles, have been used in various attempts to reduce the charge of synthetic polymeric materials by kneading or applying them to the material. Was. These methods using a conductive agent can be used when the usual amount of conductive agent used is large, when it is difficult to add them to a material, when a transparent product is obtained, or when there are mechanical and rheological properties. It is not generally feasible for a number of reasons, such as the difficulty in retaining such properties, and the high cost of such conductive agents. for that reason,
These conductive agents can only be used under some limited circumstances.

[0003] Antistatic agents are substances added to polymers to reduce their tendency to charge, and when charge is present, these antistatic agents help dissipate the charge. Antistatic agents are usually hydrophilic or ionic. When present on the surface of polymeric materials, they facilitate the transfer of electrons, thereby eliminating the build up of electrostatic charge. Antistatic agents are used in two ways. One is to use an external antistatic agent. The external antistatic agent is applied by spraying on the surface of the polymer material or immersing the polymer material. The second method uses internal antistatic agents, which are added to the polymer before processing.
The antistatic agent used in this way is required to be thermally stable and capable of moving to the surface during processing.

[0004] Since there are a large number of antistatic agents containing a surfactant as a main component, an appropriate one can be selected from them depending on the situation. In fact, a number of internally added types have been studied and tested. However, when used as an internally added antistatic agent, the anionic surfactant is inferior in compatibility and uniform dispersibility, and tends to decompose or deteriorate upon heating, so that it is difficult to handle. On the other hand, amphoteric surfactants and cationic surfactants having a quaternary nitrogen in the molecule have good antistatic properties, but are extremely poor in heat resistance and can be used only under limited circumstances. Regarding nonionic surfactants, they are relatively superior to the above-mentioned ionic surfactants in terms of compatibility with synthetic polymer materials, but tend to have weak antistatic properties, and The effect disappears with time at normal and elevated temperatures. Furthermore, because of the limited thermal stability of such nonionic surfactant-type antistatic agents, their use with engineering plastic resins such as aromatic polycarbonates is limited by the processing temperature of the resin. You. Thus, these types of surfactants adversely affect the optical properties of the aromatic polycarbonate. The metal salts of organic sulfonic acids have also been reported as internally added antistatic agents for polycarbonate and polyester resins molded especially at high temperatures, but these have insufficient compatibility with resins or insufficient heat resistance. One of the disadvantageous consequences of poor compatibility is that the transparency of certain polymeric materials such as polycarbonate is lost by the use of such antistatic agents. The use of phosphonium salts of organic sulfonic acids with halogen substituents as flame retardants has also been reported (US Pat. No. 4,093,589).
No.), they would be expected to also serve as antistatic agents.

Another patent discloses reducing electrostatic charge on polycarbonate resins. That is, U.S. Pat. No. 4,943,380 discloses an antistatic composition containing 90 to 99.9% by weight of polycarbonate and 0.1 to 10% by weight of a heat-resistant phosphonium sulfonate of the following general formula.

[0006]

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In the formula, R is a linear or branched alkyl group having 1 to 18 carbon atoms, and R ₁ , R ₂ and R ₃ are the same and are each an aliphatic group having 1 to 18 carbon atoms. A hydrocarbon group or an aromatic hydrocarbon group, wherein R ₄ has 1 to 18 carbon atoms;
Is a hydrocarbon group. Corresponding cationic surfactants containing quaternary nitrogen in the molecule have excellent antistatic properties (U.S. Pat. No. 5,468,973) but can only be used under limited circumstances due to their remarkably poor heat resistance.

[0008]

Accordingly, it is an object of the present invention to provide polycarbonates, polyetherimides, polyesters, polyphenylene ether / polystyrene blends, polyamides, polyketones, acrylonitrile-butadiene-styrene (ABS) or blends thereof or with them. An antistatic resin composition comprising a polymer such as a blend with another substance or a polymer and a heat-resistant antistatic agent, wherein the use of the antistatic agent solves the problems of the conventional antistatic agent described above. It is to provide a resin composition that can be solved.

Another object of the present invention is to provide a novel antistatic agent which can be internally added to a synthetic resin preferably having transparency in a molded state without adversely affecting the transparency and mechanical properties of a molded article. To provide. However, the present invention is not limited to transparent thermoplastic resins only, since the requirements for antistatic can be applied to colored or translucent thermoplastic polymer moldings.

[0010]

Briefly, according to the present invention, based on the total weight of polymer and additive,
About 0.05 to 10% by weight, preferably about 0.2 to 1.5
%, More preferably from about 0.5 to 1.5% by weight of certain refractory medium and short chain halogenated carbon sulfonic acid substituted phosphonium salts of from about 90 to 99.9.
5 wt%, preferably about 98.5-99.8 wt%, more preferably about 98.5-99.5 wt% polycarbonate, polyetherimide, polyester, polyphenylene ether / polystyrene blend, polyamide, polyketone, ABS Alternatively, they have found that they can be used as internal antistatic agents in these polymer resin blends. Generally, the substituted phosphonium salts of the above mentioned medium and short chain sulfonic acids have the general formula:

[0011]

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Wherein X is independently selected from halogen or hydrogen, provided that at least one X is halogen, n, m and p are integers from 0 to 12, and Y is R ₁ , R _2, and R ₃ are the same or different and each has 1 to 8 carbon atoms. An aliphatic hydrocarbon group or a carbon number of 6 to
12 aromatic hydrocarbon groups, and R ₄ has 1 to 1 carbon atoms.
18 hydrocarbon groups. Halogen may be independently selected from bromine, chlorine, fluorine and iodine. Halogen is preferably fluorine.

[0013]

DETAILED DESCRIPTION OF THE INVENTION The above phosphonium sulfonate is preferably a fluorinated phosphonium sulfonate,
It consists of a fluorocarbon-containing organic sulfonic acid anion and an organic phosphonium cation. Specific examples of such organic sulfonate anions include perfluoromethanesulfonate, perfluorobutanesulfonate, perfluorohexanesulfonate, perfluoroheptanesulfonate and perfluorooctanesulfonate. Specific examples of the above phosphonium cation, tetramethylphosphonium, tetraethylphosphonium, tetrabutylphosphonium, triethylmethylphosphonium, tributylmethylphosphonium, tributylethylphosphonium, trioctylmethylphosphonium, trimethylbutylphosphonium, trimethyloctylphosphonium, trimethyllaurylphosphonium, There are aliphatic phosphoniums such as trimethylstearylphosphonium, triethyloctylphosphonium, and aromatic phosphoniums such as tetraphenylphosphonium, triphenylmethylphosphonium, triphenylbenzylphosphonium, tributylbenzylphosphonium.

Although the fluorinated phosphonium sulfonates of the present invention can be obtained from any combination of these organic sulfonate anions and organic cations, the present invention is not limited to the above specific examples. The fluorinated phosphonium sulfonates can be prepared in a very pure state by mixing the corresponding sulfonic acids and quaternary phosphonium hydroxide in a mixed solvent and then evaporating the mixed solvent. For example, tetrabutylphosphonium perfluorobutanesulfonate is 98.6 g of perfluorobutanesulfonic acid,
40% by weight tetrabutylphosphonium hydroxide solution 200
ml and 500 ml of mixed solvent into a flask, the resulting mixture is stirred at room temperature for 1 hour, the phosphonium sulfonate which separates out as an oily layer is isolated, washed with 100 ml of water and the solvent is evaporated off by means of a vacuum pump , In a yield of about 95%.

As mentioned above, the preferred phosphonium sulfonate used in the present invention is a fluorinated phosphonium sulfonate of the general formula

[0016]

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Wherein F is fluorine and n is 1-12.
An integer, S is sulfur, R ₁, R_TwoAnd R_ThreeIs
The same aliphatic hydrocarbon groups having 1 to 8 carbon atoms each
Or an aromatic hydrocarbon group having 6 to 12 carbon atoms;
_FourIs a hydrocarbon group having 1 to 18 carbon atoms. Equation (3)
Major component is fluorinated phosphonium sulfonate represented by
Antistatic composition comprising as, its antistatic properties,
Polycarbonate is made using various methods of compatibility and heat resistance.
Sheet, polyetherimide, polyester, polyphenylene
Lenether / polystyrene blend, polyamide, poly
Suitable for liquid ketone, ABS or blends of these polymers
Antistatic properties can be imparted. The fluorocarbon sulf of the present invention
Phosphonium phonate is a low-melting semi-solid material,
It can be handled as a melt as it is. The present invention
In some embodiments, a solid crystal at room temperature (15-25 ° C.)
Quality material, weighing, handling and polycarbonate
G, polyetherimide, polyester, polyphenylene
Ether / polystyrene blend, polyamide, poly
Addition to ketones, ABS or blends of these polymers
It is easy to add.

The most common method of practicing the present invention is to directly add and mix an antistatic agent during the manufacture or processing of the polymer. It can be processed by conventional means, including extrusion, injection molding, compression molding or casting. The amount of phosphonium fluorocarbon sulfonate added to the polycarbonate, polyetherimide, polyester, polyphenylene ether / polystyrene blend, polyamide, polyketone, ABS or blend of these polymers is an amount effective to reduce or eliminate static charge. Can be changed in a wide range.
If the amount of fluorocarbon sulfonic acid-substituted phosphonium antistatic added to the resin is too low, products made from the resin will still have a tendency to charge. If the added amount of the antistatic agent is too large, the added amount is uneconomical, and if it exceeds a certain level, other properties of the resin may be adversely affected. For example, in order to obtain a favorable result by such an internal addition method in a transparent polycarbonate grade, it is preferable to add the antistatic agent of the present invention in a ratio of 0.1 to 1.5% by weight with respect to the molding composition, More preferably, it is added at a ratio of about 0.8% by weight. The antistatic agent of the present invention is more excellent in heat resistance than conventional ionic surfactants such as phosphonium alkyl sulfonate, can be added in a smaller amount, and the resin composition has excellent transparency and mechanical properties. With.

[0019]

The present invention is further described by the following examples. However, these examples do not limit the present invention at all. The percentages in the examples are percentages by weight. The following two test methods were used to analyze the antistatic behavior of the sample. They are the surface resistivity by dust absorption test, electrostatic charge measurement and electrostatic charge measurement.

Dust Absorption Test Dust absorption was developed in a transparent polycarbonate product.
In this test method, several color plates are placed in a desiccator saturated with in-situ prepared NH ₄ Cl dust. The chamber is allowed to equilibrate for one hour before placing the sample. After one hour, the sample is removed and an image of the color plate is made with a reference material using a projection lamp as a light source.
The appearance of these plates is visually compared to a polycarbonate reference plate containing no antistatic agent.

Surface resistivity The surface resistivity was measured at room temperature at a value of 10 ^17.
In the range of to 10 ¹⁸ Omega, it is difficult to obtain accurate results in such a range, were carried out at 55 ° C.. Temperature 55
The values of the surface resistivity at ° C. are in the range of 10 ¹³ to 10 ¹⁴ Ω. In addition to these tests, the following tests were also performed. Yellowness Index (YI)-ASTM 1925-63T
Measured according to. Clarity-measured according to ASTM D-1003. Haze-ASTM 1925-63T and ASTM
Measured according to D-1003. Melt Volume Rate (MVR)-ASTM D
Measured according to -1238.

Example 1 This example illustrates the preparation of a fluorinated phosphonium sulfonate of the present invention. Potassium perfluorobutyl sulfonate was used as starting material. First, an ion exchange column (Ahmbe, manufactured by Rohm & Haas)
rjet 1200H) to exchange potassium (K ⁺ ions) for H ⁺ ions. The second step used in this method was an acid-base reaction using a fluorocarbon-terminated sulfonic acid and tetrabutylphosphonium hydroxide to yield a fluorinated phosphonium sulfonate in high yield and purity. This reaction is as follows.

[0023]

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Example 2 This example illustrates the preparation of a fluorinated phosphonium sulfonate of the present invention. Potassium nonafluoroethoxyethylsulfonate was used as starting material. First, an ion exchange column (Rohm & Haas, Amb
erjet 1200H) to exchange potassium (K ⁺ ion) for H ⁺ ion. The second step used in this method was an acid-base reaction using a fluorocarbon-terminated sulfonic acid and tetrabutylphosphonium hydroxide to yield a fluorinated phosphonium sulfonate in high yield and purity.

The resulting compound had the following formula:

[0026]

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Example 3 This example illustrates the preparation of a fluorinated phosphonium sulfonate of the present invention. Zonyl-TBS (manufactured by DuPont), which is a mixture of various fluorocarbon-containing sulfonic acids and fluorocarbon-containing ammonium sulfonate, was used as a starting material. First, an ion exchange column (Rohm & Haas, Amberjet 1)
200H) was used to exchange ammonium (NH ₄ ⁺ ) for H ⁺ ions. The second step used in this method was an acid-base reaction using a fluorocarbon-terminated sulfonic acid and tetrabutylphosphonium hydroxide. The obtained compound mixture was composed of the following components (y was 1 to 9).
Integer).

[0028]

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Example 4 The antistatic properties of the fluorinated phosphonium sulfonate of Example 1 were determined. First, an antistatic agent is melt-kneaded with a transparent aromatic polycarbonate resin having an intrinsic viscosity of about 0.46 dl / g (deciliter / gram) measured in methylene chloride at 20 ° C. at a temperature of about 285 ° C. using a twin-screw extruder. The mixture was extruded through a die orifice into a strand, quenched in water, and then pelletized. The pellet was dried at about 125 ° C. for about 2 hours. Using a single-axis injection molding machine, the above-mentioned dried pellets are injected at an injection molding temperature of about 285 ° C., about 10 cm square about 2.5 mm
It was injection molded into a thick plate. Clearly, the temperature profile over the entire injection molded barrel changed to the limit of about 285 ° C. In this example, the barrel temperature varied from about 20 ° C to about 285 ° C. Each composition shown in Table 1 was produced under the same conditions as described above, and the polycarbonate concentration varies depending on the concentration of the antistatic agent present in each composition. Each composition contained the same amounts of release agent, UV absorber, stabilizer, antioxidant and dye, the total amount of which was about 0.8% by weight of the polycarbonate used. The results obtained are as follows.

[0030]

[Table 1]

The above results clearly show the excellent antistatic properties of the composition of the present invention, as shown by the results of surface resistivity and transparency, and did not affect the transparency or color. Example 5 The composition of Example 4 was molded under the more severe molding conditions of a molding temperature of + 20 ° C. of Example 4 and a cooling time of 120 seconds compared to the standard cooling time of 20 seconds of Example 4.
The results obtained are as follows.

[0032]

[Table 2]

Severe conditions (molding temperature of Example 4 + 20 ° C.)
And 12 seconds for the standard cooling time of 20 seconds in Example 4.
The results of injection molding of the same sample at each concentration using 0 second cooling time are disclosed in Table 2. Comparing the results in Tables 1 and 2, when harsh molding conditions are used, the resulting antistatic agent concentration of the antistatic polycarbonate decreases to slightly more than 0.5%. This indicates that the surface transfer ability of the antistatic agent of the present invention is improved at higher processing temperatures. This is due to the extreme temperatures (+2
(0 ° C.) at a standard cycle time (t = 20 seconds). A sample molded under standard molding and severe molding conditions with a cycle time of 20 seconds with an antistatic agent concentration of 0.6% had a surface resistivity of 1.74 (Table 1).
To 0.33 (Table 2). These results clearly show the effect of molding conditions on surface resistivity, and that the ability of the antistatic agent to migrate to the surface depends on temperature and cycle time.

Example 6 The antistatic agent used was EPA-202, a prior art phosphonium sulfonate obtained from Takemoto Yushi Co., Ltd.
Example 4 was repeated except that EPA-
The composition of Formula 202 has the following formula:
43380 is an antistatic composition.

[0035]

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The results are shown below.

[0037]

[Table 3]

The antistatic agent of the present invention (tetrabutyl phosphonium nonafluoro-1-butanesulfonate of Example 1) was replaced by the prior art phosphonium sulfonate EPA-20.
It can be seen that at a concentration much lower than 2, the antistatic properties are better. The lower the surface resistivity, the better the antistatic properties of the additive. The resistivity when the concentration of the prior art additive is 2.0% is equal when the concentration of the antistatic agent of the present invention is only 0.8%. Also, EPA-2
02 is a viscous yellow oil that increases the yellowness index, whereas the antistatic of Example 1 is a white solid, giving a better dispersion of powder than a viscous oil.

Further, as measured by MVR, the melt flow of the composition of the present invention is essentially unaffected. 1.5
Even at a concentration of% (Table 1), the MVR is only slightly above that of the composition without any additives. Table 3
With the prior art antistatic agent, the MV at a concentration of 1.5%
R is almost twice that without additives. This demonstrates that the prior art additives are acting as plasticizers and has significant adverse effects on mechanical properties (especially in aromatic polycarbonate resins).

Example 7 An intrinsic viscosity of about 0.4 measured in methylene chloride at 20 ° C.
A high flowability aromatic polycarbonate resin of 2 dl / g (deciliter / gram) was melt-kneaded under the same conditions as in Example 4 and injection-molded. However, what was molded in this example was a compact disc (CD) blank.

As described above, three kinds of compositions and three sets of CDs (10 sheets per composition) were produced by changing the polycarbonate content in accordance with the concentration of the antistatic agent present in the composition. Each composition contained the same amount of release agent and stabilizer. Sample CD blanks were examined for clarity, color, and static charge. Immediately after molding each CD blank, the static charge was measured using a calibration handheld field meter manufactured by SIMCO. The results obtained are as follows.

[0042]

[Table 4]

The above results clearly show that for very high flow grades, excellent antistatic properties can be obtained without affecting clarity and color. The composition containing 0.5% of the antistatic agent did not attract any dust in the dust absorption test. When 0.3% of the antistatic agent was added, a great improvement was observed as compared with the reference sample in which no antistatic agent was added.

Example 8 The antistatic properties of the fluorinated phosphonium sulfonates of Examples 2 and 3 (formulas (5) and (6)) were measured as follows. First, the intrinsic viscosity of the antistatic agent measured in methylene chloride at 20 ° C. is about 0.46 dl / g (deciliter / g).
G) with a twin-screw extruder to melt and knead the mixture at a temperature of about 285 ° C., extrude through a die orifice into strands, quench in water, and pelletize. The pellet was dried at about 125 ° C. for about 2 hours. Using a single-axis injection molding machine, the dried pellets were injection-molded at an injection molding temperature of about 285 ° C. into a plate of about 10 cm square and about 2.5 mm thick. Clearly, the temperature profile throughout the injection molded barrel changed to an extreme of about 285 ° C. In this example, the barrel temperature is about 20 ° C.
To about 285 ° C. Each composition shown in Table 5 was produced under the same conditions as described above, and the polycarbonate concentration varies depending on the concentration of the antistatic agent present in each composition. Each composition contained the same amounts of release agent, UV absorber, stabilizer, antioxidant and dye, the total amount of which was about 0.8% by weight of the polycarbonate used. The results obtained are as follows.

[0045]

[Table 5]

As is evident from the above examples, the use of the antistatic composition of the present invention allows the use of the prior art EP described in Example 6.
It clearly shows that the surface resistivity of the formed plate is low even with a small amount of addition as compared with A-202. Furthermore, EPA-
In 202, severe yellowing occurred under severe molding conditions, whereas no such yellowing was observed in the novel synthetic antistatic composition of the present invention. Also, EPA-20
2 was regarded as a plasticizer for polycarbonate as seen in the increase in MVR value, whereas essentially no change in flow was observed with the fluorinated phosphonium sulfonates of the present invention.

In the present invention, it will be understood by those skilled in the art that various modifications can be made to the above-described embodiment without departing from the spirit and scope of the invention defined in the claims of the present application. .

Continuing on the front page (72) Inventor Theodoras Lambertas Hawks The Netherlands, 4613, AS Bergen op Sohm, Halstersweg, No. 303

Claims (10)

[Claims] 1. An antistatic thermoplastic resin composition comprising a mixture of an antistatic agent comprising a halogenated carbon sulfonate of a polysubstituted phosphonium compound and a thermoplastic resin, wherein the phosphonium compound is a thermoplastic resin. A thermoplastic resin composition present in an amount sufficient to impart antistatic properties to articles molded from the thermoplastic resin composition. 2. The composition according to claim 1, wherein the antistatic agent is a fluorinated carbon sulfonate of a polysubstituted phosphonium compound. 3. The thermoplastic resin is an aromatic polycarbonate, polyetherimide, polyester, polyphenylene ether, polyphenylene ether / styrene polymer blend, polyamide, polyketone, acrylonitrile-butadiene-styrene, blends thereof and other materials. The composition of claim 1, wherein the composition is selected from the group consisting of a blend with 4. The composition according to claim 1, wherein the thermoplastic resin composition comprises 90 to 99.95% by weight based on the weight of the thermoplastic resin and additives.
The composition according to claim 1, comprising a thermoplastic resin of the formula (1) and a corresponding 10 to 0.05% by weight of an antistatic agent. 5. The composition according to claim 2, wherein the fluorinated carbon sulfonate of the polysubstituted phosphonium compound is a fluorinated phosphonium sulfonate compound of the following formula. Embedded image Wherein n is an integer of 0 to 18, and R ₁ , R ₂ and R ₃
Are the same and are each selected from the group consisting essentially of an aliphatic hydrocarbon group having 1 to 8 carbon atoms and an aromatic hydrocarbon group having 6 to 12 carbon atoms, and R ₄ is a carbon atom These are hydrocarbon groups of the formulas 1 to 18. 6. The composition of claim 5, wherein said fluorinated phosphonium sulfonate compound is of the formula: Embedded image 7. The composition according to claim 5, wherein said thermoplastic resin is a transparent aromatic polycarbonate. 8. An antistatic compound of the following formula: Embedded image Wherein X is independently selected from the group consisting essentially of halogen and hydrogen, provided that at least one X is halogen, and n, m and p are integers from 0 to 12 , Y is absent or selected from the group consisting of heterocyclic atoms other than carbon in the atomic ring or nitrogen, oxygen, sulfur, selenium, phosphorus, arsenic, etc., and R ₁ , R ₂
And R ₃ are the same and are each independently selected from the group consisting essentially of an aliphatic hydrocarbon group having 1 to 8 carbon atoms and an aromatic hydrocarbon group having 6 to 12 carbon atoms,
R ₄ is a hydrocarbon group having 1 to 18 carbon atoms, and the halogen is independently selected from the group consisting essentially of bromine, chlorine, fluorine and iodine. 9. The compound according to claim 8, wherein X is fluorine. 10. n is 3, R ₁ , R ₂ , R ₃ and R ₄
Are each an alkyl group having 4 carbon atoms, Y is absent, m
And p is zero.